Process for trichromatic dyeing or printing of polyamide

ABSTRACT

A process for dyeing or printing natural and synthetic polyamide material by the trichromatic technique, which comprises the use of a red dye of the formula (1) defined in the specification, or a mixture of the red dye of the formula (1) with a red dye of the formula (2) together with at least one yellow or orange dye of the formula (3), or a mixture of at least one yellow or orange dye of the formula (3) with a yellow dye of the formula (4) and at least one blue dye of the formula (5). The process of the invention is suitable for dyeing natural or synthetic polyamide material from an aqueous liquor or for printing with printing pastes. It is particularly suitable for dyeing from short liquors.

It is the object of the present invention to provide a process fordyeing and printing natural and synthetic polyamide material with dyessuitable for combination dyeing by the trichromatic technique. The dyesto be used in the process of this invention shall have a level colourbuild-up, while at the same time ensuring a constant shade at differentconcentrations, and they shall also have good compatibility. It has nowbeen found that the process of this invention meets these requirements.

According, the present invention relates to a process for dyeing orprinting natural and synthetic polyamide materials by the trichromaticdyeing technique with mixtures of dyes, which process comprises the useof a red dye of the formula ##STR1## wherein A is hydrogen,unsubstituted or substituted C₁ -C₄ alkyl, ##STR2## or --SO₂ R₃, whereinR₁ is C₁ -C₄ alkyl, R₂ is unsubstituted or substituted C₅ -C₇ cycloalkylor unsubstituted or substituted phenyl, and R₃ is unsubstituted orsubstituted phenyl or unsubstituted or substituted phenoxy, and B ishydrogen, halogen, C₂ -C₄ alkanoylamino, C₅ -C₈cycloalkoxycarbonylamino, C₁ -C₄ alkoxycarbonylamino, C₁ -C₄alkylsulfonylamino or unsubstituted or substituted phenylsulfonylamino,or a mixture of the red dye of the formula (1) with a red dye of theformula ##STR3## wherein R₄ is methyl or ethyl and R₅ is cyclohexyl orphenyl, together with at least one yellow or orange dye of the formula##STR4## wherein B₁, B₂ and E₁ are hydrogen, C₁ -C₄ alkyl or C₁ -C₄alkoxy, and X is straight chain or branched C₁ -C₄ alkyl or straightchain or branched C₂ -C₄ hydroxyalkyl, or a mixture of at least oneyellow or orange dye of the formula (3) with a yellow dye of the formula##STR5## wherein Z₁, Z₂ and Z₃ are independently hydrogen, halogen, C₁-C₄ alkyl or C₁ -C₄ alkoxy, and at least one blue dye of the formula##STR6## wherein one Y is hydrogen or methyl and the other Y is C₂ -C₄alkanoylamino or C₂ -C₄ hydroxyalkylsulfamoyl, and Z₄ is hydrogen ormethyl.

By the trichromatic dyeing technique is meant the additive blending ofsuitably chosen yellow or orange, red and blue dyes with which eachdesired shade of the visible colour spectrum may be adjusted byappropriate choice of the quantity ratios.

Suitable alkyl radicals A, B₁, B₂, E₁, R₁, X, Z₁, Z₂ and Z₃ in formulae(1), (3) and (4) are, independently of one another, straight chain orbranched alkyl radicals, for example methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, isobutyl and tert-butyl.

The alkyl radical A may be substituted e.g. by halogen such as chlorineor bromine and, in particular, fluorine. The alkyl radical A ispreferably a C₁ -C₄ perfluoroalkyl radical, most preferably thetrifluoromethyl radical.

A suitable C₅ -C₇ cycloalkyl radical R₂ is e.g. the cyclohexyl radicalor an alkyl-substituted, for example a methyl-substituted, cyclohexylradical.

An unsubstituted or substituted phenyl radical R₂ or R₃ is a phenylradical which is substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen,but is preferably an unsubstituted phenyl radical.

An unsubstituted or substituted phenoxy radical R₃ may be a phenoxyradical which is substituted by C₁ -C₄ alkyl, preferably methyl, or C₁-C₄ alkoxy, or by halogen, preferably chlorine. A phenoxy radical R₃ ispreferably an unsubstituted or a chlorine-substituted phenoxy radical.

B, Z₁, Z₂ and Z₃ as halogen in formulae (1) and (4) may be fluorine orbromine and preferably chlorine.

B and Y as C₂ -C₄ alkanoylamino in formulae (1) and (5) may be theacetylamino, propionylamino or butyrylamino radical.

B as C₅ -C₈ cycloalkoxycarbonylamino is in particular thecyclohexyloxycarbonylamino radical.

B as C₁ -C₄ alkylsulfonylamino is the methylsulfonylamino,ethylsulfonylamino, propylsulfonylamino, butylsulfonylamino,tert-butylsulfonylamino, isobutylsulfonylamino or sec-butylsulfonylaminoradical.

B as a phenylsulfonylamino radical may be a phenylsulfonylamino radicalwhich is substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen, but ispreferably an unsubstituted or a methyl-substituted phenylsulfonylaminoradical.

Suitable alkoxy radicals for B₁, B₂, E₁, Z₁, Z₂ and Z₃ in formulae (3)and (4) are e.g. the methoxy, ethoxy, propoxy, isopropoxy, butoxy,sec-butoxy, isobutoxy or tert-butoxy radical.

A suitable hydroxyalkyl radical X in formula (3) is a straight chain orbranched hydroxyalkyl radical, for example the β-hydroxyethyl,β-hydroxypropyl, β-hydroxybutyl or α-ethyl-β-hydroxyethyl radical.

A C₂ -C₄ hydroxyalkylsulfamoyl radical Y in formula (5) is e.g. theβ-hydroxyethylsulfamoyl, β-hydroxypropylsulfamoyl,γ-hydroxypropylsulfamoyl or the β-hydroxybutylsulfamoyl radical.

If mixtures of the red dyes of the formulae (1) and (2) are used in theprocess of this invention, the ratio of dyes of the formula (1) to thoseof the formula (2) is 90:10 to 10:90 and preferably 70:30 to 30:70.

Important process variants comprise using:

(a) a red dye of the formula (1), wherein A is hydrogen, methyl,trifluoromethyl, ##STR7## or --SO₂ R₃, in which R₁ is methyl or ethyl,R₂ is cyclohexyl or phenyl, and R₃ is phenyl, methylphenyl, phenoxy orchlorophenoxy, and B is hydrogen, chlorine, acetylamino, propionylamino,cyclohexyloxycarbonylamino, phenylsulfonylamino ormethylphenylsulfonylamino, with the proviso that A and B together arenot both hydrogen;

(b) a red dye of the formula (1), wherein A and B are as defined in (a),together with the red dye of the formula ##STR8##

(c) a red dye of the formula (1), wherein A and B are as defined in (a),together with the red dye of the formula ##STR9##

(d) a red dye of the formula (1), wherein A is hydrogen, phenylsulfonyl,phenoxysulfonyl or trifluoromethyl, and B is hydrogen, acetylamino orcyclohexyloxycarbonylamino;

(e) a red dye of the formula (1) wherein A is hydrogen, and B isacetylamino or cyclohexyloxycarbonylamino, or A is trifluoromethyl and Bis acetylamino, or A is phenylsulfonyl or phenoxysulfonyl, and B ishydrogen.

As yellow or orange dye of the formula (3) it is preferred to use a dyeof the formula ##STR10## wherein A₁ is hydrogen or methyl, F₁ ishydrogen or methyl and X₁ is methyl, ethyl, β-hydroxyethyl,β-hydroxypropyl, β-hydroxybutyl or α-ethyl-β-hydroxyethyl.

As dye of the formule (4) it is preferred to use a dye of the formula##STR11## wherein each of Z₅ and Z₆ independently is hydrogen, methyl orchlorine.

It is particularly preferred to use the yellow dye of the formula##STR12## a mixture of the yellow dye of the formula (10) with theorange dye of the formula ##STR13## or a mixture of the dyes of theformulae (10) and (11) with the dye of the formula ##STR14## the ratioof the dyes of the formulae (10) and (11) being 60:40 to 40:60 andpreferably 1:1, and the ratio of the dyes of the formulae (10), (11) and(12) being 60:20:20, 20:60:20 to 20:20:60 and preferably 1:1:1.

As blue dye of the formula (5) it is preferred to use a dye of theformula ##STR15## wherein one Y₁ is hydrogen or methyl and the other Y₁is acetylamino, propionylamino or C₂ -C₄ hydroxyalkylsulfamoyl, and Z₇is hydrogen or methyl, or a mixture of the blue dyes of the formulae##STR16## wherein Y₂ is a C₂ -C₄ hydroxyalkylsulfamoyl radical, and##STR17## and, in particular, the dyes of the formulae ##STR18## or amixture of a dye of the formula (16) or (17) with a dye of the formula(18) or (19).

The particularly preferred process variants comprise using a red dye ofthe formula (1), wherein A is hydrogen and B is acetylamino orcyclohexyloxycarbonylamino, or A is trifluoromethyl and B isacetylamino, or A is phenylsulfonyl or phenoxysulfonyl and B ishydrogen, optionally in admixture with a red dye of the formula (2),wherein R₄ is methyl and R₅ is cyclohexyl, or R₄ is ethyl and R₅ isphenyl, together with the yellow dye of the formula (10) or with amixture of the yellow dye of the formula (10) and the orange dye of theformula (11), or with a mixture of the dyes of the formulae (10) and(11) with the dye of the formula (12), the ratio of the dyes of theformulae (10) to (12) being 1:1 or 1:1:1, and with one of the blue dyesof the formulae (16) and (20) or with a mixture of the blue dye of theformula (16) with a dye of the formula (15), the ratio of the dyes ofthe formulae (16) and (15) being 60:40 to 40:60.

The most preferred process variant comprises using a red dye of theformula (1), wherein A is trifluoromethyl and B is acetylamino, togetherwith the yellow dye of the formula (10) or with the orange dye of theformulae (11) or with a mixture of the yellow or orange dyes of theformulae (10), (11) and (12), the ratio of the dyes of the formulae (10)to (12) being 1:1:1, and with one of the blue dyes of the formulae (16)and (20) or with a mixture of the blue dye of the formula (16) with theblue dye of the formula (18), the ratio of the dyes of the formulae (16)and (18) being 60:40 to 40:60.

Another preferred process variant comprises using a red dye of theformula (1) together with at least one yellow or orange dye of theformula (3) or with a mixture of at least one yellow or orange dye ofthe formula (3) with a yellow dye of the formula (4) and at least oneblue dye of the formula (5).

The dyes employed in the process for trichromatic dyeing or printing areknown or they may be prepared by methods similar to known ones. Forexample, the dyes of the formulae (1) and (2) may be obtained inaccordance with the particulars of German patent specifications Nos. 702932 and 2 063 907 and the German Offenlegungsschrift No. 2 712 170,those of the formula (5) in accordance with the particulars of U.S. Pat.Nos. 3,778,453 and 1,927,125, and those of the formulae (3) and (4) inaccordance with the particulars of German Offenlegungsschrift No. 2 142412 and German Auslegeschrift No. 1 100 846.

If mixtures of dyes are used in the process of this invention, these maybe prepared by mixing the individual dyes. Mixing is effected e.g. insuitable mills, e.g. ball mills and disc attrition mills, as well as inkneaders or mixers. Further, the dyestuff mixtures may be obtained byspray drying the aqueous dyestuff mixtures.

The dyes employed in the process of the invention are either in the formof their free sulfonic acids or, preferably, of their salts.

Examples of suitable salts are the alkali metal salts, alkaline earthmetal salts or ammonium salts, or the salts of an organic amine. Typicalexamples are the sodium, lithium, potassium or ammonium salts or thesalt of triethanolamine.

The dyes employed in the process of the invention usually containfurther auxiliaries, e.g. sodium chloride or dextrin.

The trichromatic dyeing or printing process of this invention issusceptible of application to conventional dyeing or printing methods.In addition to containing water and the dyes, the dye liquors orprinting pastes may contain further auxiliaries, e.g. wetting agents,antifoams, levelling agents or agents which influence thecharacteristics of the textile material, e.g. softeners, flameproofingadditives, or dirt, water and oil repellents, as well as water softenersand natural or synthetic thickeners, e.g. alginates and celluloseethers.

The process of this invention is especially suitable for dyeing fromshort liquors, e.g. in continuous dyeing or discontinuous and continuousfoam dyeing processes.

In trichromatic dyeing or printing, the dyes employed in the process ofthis invention are distinguished by level colour build-up, goodexhaustion properties, good constancy of shade even at differentconcentrations, good fastness properties, and in particular by very goodcompatibility.

The process of this invention is suitable for dyeing or printing bothnatural polyamide material, e.g. wool, and, in particular, syntheticpolyamide material, e.g. perlon or nylon, and is suitable for dyeing orprinting blends or yarns of wool and synthetic polyamide. The textilematerial may be in the most widely different forms of processing, e.g.in the form of fibre, yarn, wovens or knits and, in particular, ofcarpets.

In the following Examples, parts are by weight. The relationship betweenparts by weight and parts by volume is the same as that between the gramand the cubic centimeter.

EXAMPLE 1

10 parts of Helanca knitted fabric are dyed in 500 parts of an aqueousliquor which contains 2 g/l of ammonium acetate and which is adjusted topH 5 with acetic acid. The dyes used are: 0.2% of the red dye of theformula ##STR19## 0.6% of the orange dye of the formula ##STR20## and0.1% of the mixture of blue dyes comprising 56.6 parts of the dye of theformula ##STR21## and 43.4 parts of the dye of the formula ##STR22## theamounts being based on the weight of the fabric.

The dyeing time at a temperature of 98° C. is 30 to 90 minutes. The dyedknitted fabric is then removed from the liquor and rinsed and dried inthe usual manner. The fabric is dyed in a completely level reddish brown(henna brown) shade with no trace of material-induced barriness.

Fabrics completely levelly dyed in the indicated shade is obtained byusing the red dyes and mixtures of dyes listed in the following tableinstead of 0.2% of the red dye of this Example, and otherwise carryingout the same procedure.

                  TABLE 1                                                         ______________________________________                                        Example Dye                     Shade                                         ______________________________________                                                 ##STR23##              reddish brown                                 3                                                                                      ##STR24##              reddish brown                                 4                                                                                      ##STR25##              reddish brown                                 5                                                                                      ##STR26##              reddish brown                                 6       mixture of 30 parts of the dye                                                 ##STR27##              reddish brown                                         and 70 parts of the dye                                                        ##STR28##                                                            7       mixture of 50 parts of the dye                                                 ##STR29##              reddish brown                                         and 50 parts of the dye                                                        ##STR30##                                                            8       mixture of 50 parts of the dye                                                 ##STR31##              reddish brown                                         and 50 parts of the dye                                                        ##STR32##                                                            9       mixture of 20 parts of the dye                                                 ##STR33##              reddish brown                                         and 80 parts of the dye                                                        ##STR34##                                                            10      mixture of 20 parts of the dye                                                 ##STR35##              reddish brown                                         and 80 parts of the dye                                                        ##STR36##                                                            ______________________________________                                    

EXAMPLE 11

10 parts of polyamide 66 yarn are dyed in 400 parts of an aqueous liquorwhich contains 1.5 g/l of ammonium acetate and which is adjusted to pH5.5 with acetic acid. The dyes used are: 0.47% of the dye of the formula##STR37## 0.45% of the dye of the formula ##STR38## and 0.17% of the dyeof the formula ##STR39## the amounts being based on the weight of thefabric. The dyebath is heated to 98° C. over the course of 30 minutesand kept for 60 minutes at 95°-98° C. The dyed yarn is then removed fromthe liquor and rinsed and dried in the usual manner. The yarn is dyed ina reddish brown (rust brown) shade.

EXAMPLE 12

10 parts of polyamide 66 yarn are dyed in 400 parts of an aqueous liquorwhich contains 1.5 g/l of ammonium acetate and which is adjusted to pH5.5 with acetic acid. The dyes used are:

0.47% of the red dye of the formula ##STR40## 0.45% of the yellow dye ofthe formula ##STR41## and 0.17% of the mixture of blue dyes comprising52 parts of the dye of the formula ##STR42## and 48 parts of the dye ofthe formula ##STR43## the amounts being based on the weight of thefabric. The dyebath is heated to 98° C. over the course of 30 minutesand kept for 60 minutes at 96°-98° C. The dyed yarn is then removed fromthe liquor and rinsed and dried in the usual manner. The yarn is dyed ina reddish brown (rust brown) shade.

Yarn completely levelly dyed in the indicated shade is obtained by usingthe red dyes and mixtures of dyes listed in the following Table insteadof the 0.47% of red dye used in this Example, and otherwise carrying outthe same procedure.

                  TABLE 2                                                         ______________________________________                                        Example Dye                     Shade                                         ______________________________________                                        13                                                                                     ##STR44##              rust                                          14                                                                                     ##STR45##              rust                                          15                                                                                     ##STR46##              rust                                          16                                                                                     ##STR47##              rust                                          17      mixture of 40 parts of the dye                                                 ##STR48##              rust                                                  and 60 parts of the dye                                                        ##STR49##                                                            18      mixture of 20 parts of the dye                                                 ##STR50##              rust                                                  and 80 parts of the dye                                                        ##STR51##                                                            19      mixture of 50 parts of the dye                                                 ##STR52##              rust                                                  and 50 parts of the dye                                                        ##STR53##                                                            20      mixture of 20 parts of the dye                                                 ##STR54##              rust                                                  and 80 parts of the dye                                                        ##STR55##                                                            21      mixture of 20 parts of the dye                                                 ##STR56##              rust                                                  and 80 parts of the dye                                                        ##STR57##                                                            ______________________________________                                    

EXAMPLE 22

500 m² of a polyamide 66 cut-pile carped (brushed goods backed withpolypropylene tape fabric) having a weight of 535 g/m² are continuouslyprewetted in a liquor which contains 1 g/liter of the polyadduct of 1mole of nonylphenol and 9 moles of ethylene oxide, and then expressed toa pick-up of 40% by weight.

A dye foam having a blow ratio of 1:10 is prepared in a mixer from anaqueous liquor of the following composition:

0.45 g/l of the red dye of the formula ##STR58## 0.9 g/l of the mixtureof yellow dyes comprising the dyes of the formulae ##STR59## in theratio 1:1, and 0.3 g/l of the blue dye of the formula ##STR60## 2.5 g/lof a foam stabiliser mixture consisting of coconut fatty aciddiethanolamide/nonylphenol polyglycol(11) ether and sodium lauryltriglycol ether sulfate,

0.6 g/l of the oxyalkylene-siloxane copolymer of the formula ##STR61##g/l of sodium acetate, and acetic acid for adjusting the pH value of theliquor to 6.

This foam is then applied from a container, equipped with a knife foradjusting the desired thickness of the foam, via an applicator rollusing a carriage to the pile side of the carpet which passes through thedyeing unit at a rate of 9 m/minute. The height of the foam is 8 mm. Thefoam add-on is 135%.

A vacuum (˜0.1 bar) is then applied to the back of the carpet in orderto effect partial penetration of the layer of foam into the carpet,whereby the height of the foam is somewhat reduced. The carpet thenpasses over a conveyor roll into a steamer (102° C., saturated steam),where the foam rises slightly and is then collapsed. The carpet issubsequently spayed with water of 80° C., then centrifuged, and dried at100°-130° C. in a cylindrical sieve drier.

The carpet fabric is dyed in a level beige shade with excellentpenetration of the dye. The foam dyeing has a positive influence on thesoftness and bulk of the fabric.

Carpet material which is completely levelly dyed in the indicated shadeis obtained by using the red dyes and mixtures of dyes indicated in thefollowing table instead of 0.45 g/l of the red dye in this Example andotherwise carrying out the same procedure.

                  TABLE 3                                                         ______________________________________                                        Example                                                                              Dye                      Shade                                         ______________________________________                                        23                                                                                    ##STR62##               beige                                         24                                                                                    ##STR63##               beige                                         25                                                                                    ##STR64##               beige                                         26                                                                                    ##STR65##               beige                                         27     mixture of 40 parts of the dye                                                                         beige                                                 ##STR66##                                                                    and 60 parts of the dye                                                        ##STR67##                                                             28     mixture of 30 parts of the dye                                                                         beige                                                 ##STR68##                                                                    and 70 parts of the dye                                                        ##STR69##                                                             29     mixture of 60 parts of the dye                                                                         beige                                                 ##STR70##                                                                    and 40 parts of the dye                                                        ##STR71##                                                             30     mixture of 10 parts of the dye                                                                         beige                                                 ##STR72##                                                                    and 90 parts of the dye                                                        ##STR73##                                                             31     mixture of 20 parts of the dye                                                                         beige                                                 ##STR74##                                                                    and 80 parts of the dye                                                        ##STR75##                                                             ______________________________________                                    

EXAMPLE 32 (Carpet printing)

A polyamide 6 cut-pile fitted carpet having a weight of 350 to 400 g/m²is impregnated on a padder with a padding liquor consisting of 988 partsof water, 10 parts of 36° Be sodium hydroxide solution and 2 parts ofwetting agent, and pinched off to a pick-up of 80%.

A dye paste of the following composition is sprayed in the form of apattern, by means of a nozzle, onto the pretreated carpet:

942 parts of water

50 parts of thickener

3 parts of antifoam

5 parts of the red mixture comprising 30 parts of the dye of the formula##STR76## and 70 parts of the dye of the formula ##STR77## 1.5 parts ofthe mixture comprising the dyes of the formulae ##STR78## in the ratio1:1:1, and 1 part of the mixture of blue dyes comprising 52 parts of thedye of the formula ##STR79## and 48 parts of the dye of the formula##STR80##

The thickener used has the following composition:

240 parts of white spirit,

50 parts of a water-in-oil emulsifier,

20 parts of an oil-in-water emulsifier,

20 parts of an antifoam,

50 parts of a crosslinked carboxyvinyl polymer having a molecular weightof approx. 4,000,000,

70 parts of a linear carboxyvinyl polymer having a molecular weight ofapprox. 1,000,000, and

550 parts of water,

the pH having been adjusted to a value of 4.5 with acetic acid.

The material which has been sprayed with the dye paste is then treatedwith saturated steam at 101° C. for 5 minutes in order to fix the dyes,then rinsed, neutralised, rinsed again and dried.

A bordeaux pattern with very sharp contours is obtained on the cut-pilefitted carpet. Dye penetration is very good and there is absolutely nofrosting.

EXAMPLE 33 (Continuous carpet dyeing)

2.7 parts of the yellow dyestuff mixture of Example 32, 1.2 parts of thered dye of Example 1 and 1.3 parts of the mixture of blue dyes ofExample 32 are dissolved in 100 parts of water by brief boiling. Thissolution is then added to a solution containing 3 parts of a thickenerbased on locust bean gum, 5.0 parts of a coacervate-forming paddingassistant based on a condensation product of a higher-molecular fattyacid with an oxyalkylamine, 2.0 parts of crystalline monosodiumphosphate and 1.0 part of crystalline disodium phosphate in 500 parts ofcold water. The mixture is then bulked to 1000 parts with cold water.300% (based on the weight of carpet) of this liquor, which has a pHvalue of 5.5 to 6.5, are then applied to a polyamide tufted undyedcarpet, at a carpet speed of 8 meters per minute. The impregnated carpetis passed into a festoon steamer, where it is treated for 10 minuteswith saturated steam at 98° to 100° C. The carpet is then washed in anopen width washing machine. It is dyed in a neutral brown shade.

Carpets which are completely levelly dyed in the indicated shade areobtained by using the dyes and dyestuff mixtures in Table 4 instead of 5parts of the red dye employed in this Example and otherwise carrying outthe same procedure.

                  TABLE 4                                                         ______________________________________                                        Example                                                                              Dye                      Shade                                         ______________________________________                                        34                                                                                    ##STR81##               bordeaux                                      35                                                                                    ##STR82##               bordeaux                                      36                                                                                    ##STR83##               bordeaux                                      37                                                                                    ##STR84##               bordeaux                                      38     mixture of 50 parts of the dye                                                                         bordeaux                                              ##STR85##                                                                    and 50 parts of the dye                                                        ##STR86##                                                             39     mixture of 50 parts of the dye                                                                         bordeaux                                              ##STR87##                                                                    and 50 parts of the dye                                                        ##STR88##                                                             40     mixture of 80 parts of the dye                                                                         bordeaux                                              ##STR89##                                                                    20 parts of the dye                                                            ##STR90##                                                             41     mixture of 20 parts of the dye                                                                         bordeaux                                              ##STR91##                                                                    and 80 parts of the dye                                                        ##STR92##                                                             42     mixture of 20 parts of the dye                                                                         bordeaux                                              ##STR93##                                                                    and 80 parts of the dye                                                        ##STR94##                                                             ______________________________________                                    

EXAMPLE 43

The procedure of Example 11 is repeated, except that 0.17% of the bluedye of the formula ##STR95## is used instead of 0.17% of the blue dye ofthe formula indicated in Example 11. The yarn is dyed in a reddish brown(rust brown) shade.

EXAMPLE 44 (Continuous wool dyeing)

A woollen material is padded with a liquor containing 0.3 part of thedyestuff mixture of Example 22, 11.0 parts of the red dyestuff mixtureof Example 6, 10.0 parts of the blue dyestuff mixture of Example 1, 2.0parts of an alginate thickener, 22.0 parts of a coacervate-formingpadding agent based on a condensation product of a higher-molecularfatty acid with a hydroxyalkylamine, and 8.0 parts of 80% formic acid in1000 parts of water. The pick-up is 85%, based on the weight of thewool. The material is then steamed for 15 minutes in saturated steam at98° to 100° C. and then washed.

A level violet dyeing is obtained.

EXAMPLE 45

The procedure of Example 11 is repeated, except that 0.46% of the yellowdye of the formula ##STR96## is used instead of 0.45% of the yellow dyeof the formula indicated in Example 11. The yarn is dyed in a reddishbrown shade.

What is claimed is:
 1. A process for dyeing or printing natural andsynthetic polyamide material by the trichromatic technique, whichcomprises the use of a red dye of the formula ##STR97## wherein A ishydrogen, unsubstituted or substituted C₁ -C₄ alkyl, ##STR98## or --SO₂R₃, wherein R₁ is C₁ -C₄ alkyl, R₂ is unsubstituted or substituted C₅-C₇ cycloalkyl or unsubstituted or substituted phenyl, and R₃ isunsubstituted or substituted phenyl or unsubstituted or substitutedphenoxy, and B is hydrogen, C₂ -C₄ alkanoylamino, C₅ -C₈cycloalkoxycarbonylamino, C₁ -C₄ alkoxycarbonylamino, C₁ -C₄alkylsulfonylamino or unsubstituted or substituted phenylsulfonylamino,or a mixture of the red dye of the formula (1) with a red dye of theformula ##STR99## wherein R₄ is methyl or ethyl and R₅ is cyclohexyl orphenyl, together with at least one yellow or orange dye of the formula##STR100## wherein B₁, B₂ and E₁ are hydrogen, C₁ -C₄ alkyl or C₁ -C₄alkoxy, and X is straight chain or branched C₁ -C₄ alkyl or straightchain or branched C₂ -C₄ hydroxyalkyl, or a mixture of at least oneyellow or orange dye of the formula (3) with a yellow dye of the formula##STR101## wherein Z₁, Z₂ and Z₃ are each independently hydrogen,halogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy, and at least one blue dye of theformula ##STR102## wherein one Y is hydrogen or methyl and the other Yis C₂ -C₄ alkanoylamino or C₂ -C₄ hydroxyalkylsulfamoyl and Z₄ ishydrogen or methyl.
 2. A process according to claim 1, which comprisesthe use of a red dye of the formula (1), wherein A is hydrogen, methyl,trifluoromethyl, ##STR103## or --SO₂ R₃, in which R₁ is methyl or ethyl,R₂ is cyclohexyl or phenyl, and R₃ is phenyl, methylphenyl, phenoxy orchlorophenoxy, and B is hydrogen, acetylamino, propionylamino,cyclohexyloxycarbonylamino, phenylsulfonylamino ormethylphenylsulfonylamino, with the proviso that A and B together arenot both hydrogen.
 3. A process according to claim 2, which comprisesthe use of a red dye of the formula (1), wherein A and B are as definedin claim 2, together with the red dye of the formula ##STR104##
 4. Aprocess according to claim 2, which comprises the use of a red dye ofthe formula (1), wherein A and B are as defined in claim 2, togetherwith the red dye of the formula ##STR105##
 5. A process according toclaim 2, which comprises the use of a red dye of the formula (1),wherein A is hydrogen, phenylsulfonyl, phenoxysulfonyl ortrifluoromethyl, and B is hydrogen, acetylamino orcyclohexyloxycarbonylamino.
 6. A process according to claim 5, whichcomprises the use of a red dye of the formula (1), wherein A is hydrogenand B is acetylamino or cyclohexyloxycarbonylamino, or A istrifluoromethyl and B is acetylamino, or A is phenylsulfonyl orphenoxysulfonyl and B is hydrogen.
 7. A process according to claim 1,which comprises the use of at least one yellow or orange dye of theformula ##STR106## wherein A₁ is hydrogen or methyl, F₁ is hydrogen ormethyl and X₁ is methyl, ethyl, β-hydroxyethyl, β-hydroxypropyl,β-hydroxybutyl or α-ethyl-β-hydroxyethyl, or a mixture of at least onedye of the formula (8) and a yellow dye of the formula ##STR107##wherein Z₅ and Z₆ are each independently hydrogen, methyl or chlorine.8. A process according to claim 7, which comprises the use of the yellowdye of the formula ##STR108## a mixture of the yellow dye of the formula(10) with the orange dye of the formula ##STR109## or a mixture of thedyes of the formulae (10) and (11) with the dye of the formula##STR110## the ratio of the dyes of the formulae (10) and (11) being60:40 to 40:60: and preferably 1:1, and the ratio of the dyes of theformulae (10), (11) and (12) being 60:20:20, 20:60:20 to 20:20:60 andpreferably 1:1:1.
 9. A process according to claim 1, which comprises theuse of a blue dye of the formula ##STR111## wherein one Y₁ is hydrogenor methyl and the other Y₁ is acetylamino, propionylamino or C₂ -C₄hydroxyalkylsulfamoyl, and Z₇ is hydrogen or methyl, or a mixture of theblue dyes of the formulae ##STR112## wherein Y₂ is a C₂ -C₄hydroxyalkylsulfamoyl radical, and ##STR113##
 10. A process according toclaim 9, which comprises the use of a blue dye of the formulae##STR114## or a mixture of a dye of the formulae (16) or (17) with a dyeof the formula (18) or (19).
 11. A process according to claim 1, whichcomprises the use of a red dye of the formula (1), wherein A is hydrogenand B is acetylamino or cyclohexyloxycarbonylamino, or A istrifluoromethyl and B is acetylamino, or A is phenylsulfonyl orphenoxysulfonyl and B is hydrogen, optionally in admixture with a reddye of the formula (2), wherein R₄ is methyl and R₅ is cyclohexyl, or R₄is ethyl and R₅ is phenyl, together with the yellow dye of the formula(10) ##STR115## or with a mixture of the yellow dye of the formula (10)and of the orange dye of the formula (11), ##STR116## or with a mixtureof the dyes of the formulae (10) and (11) with the dye of the formula(12), ##STR117## the ratio of the dyes of the formulae (10) to (12)being 1:1 or 1:1:1, and with one of the blue dyes of the formulae##STR118## or with a mixture of the blue dye of the formula (16) with adye of the formula ##STR119## the ratio of the dyes of the formulae (16)and (15) being 60:40 to 40:60.
 12. A process according to claim 1, whichcomprises the use of a red dye of the formula (1), wherein A istrifluoromethyl and B is acetylamino, together with the yellow dye ofthe formula ##STR120## or with the orange dye of the formula ##STR121##or with a mixture of the dyes of the formulae (10) and (11) with the dyeof the formula ##STR122## the ratio of the dyes of the formulae (10) to(12) being 1:1:1, and with one of the blue dyes of the formulae##STR123## or with a mixture of the blue dye of the formula (16) withthe blue dye of the formula ##STR124## the ratio of the dyes of theformulae (16) and (18) being 60:40 to 40:60.
 13. A process according toclaim 1 for dyeing or printing material made from natural and syntheticpolyamide by the trichromatic technique, which process comprisestreating said material with a dye liquor or printing paste whichcontains the dyestuff mixture according to claim 1, together with waterand optionally further auxiliaries.
 14. An aqueous dye liquor orprinting paste which contains the dyestuff mixture according to claim 1and optionally further auxiliaries.
 15. A material dyed or printed bythe process according to claim
 13. 16. A polyamide material dyed orprinted according to claim
 15. 17. A dyed material according to claim 15wherein the material is a textile material.
 18. A polyamide materialaccording to claim 16 wherein the material is a polyamide carpetmaterial.